GeH_4与HX(X=F,Cl,Br)间二氢键复合物的理论研究  

Theoretical study on dihydrogen bond of GeH_4 with HX(X=F,Cl,Br)

作　　者：刘红[1] 陈燕芹[1] 

机构地区：[1]贵州省毕节学院化学系,贵州毕节551700

出　　处：《分子科学学报》2011年第5期348-353,共6页Journal of Molecular Science

基　　金：贵州省教育厅自然科学研究基金资助项目(2008075);毕节学院科学研究基金资助项目(20082006)

摘　　要：对GeH4与HX形成的二氢键复合物的结构特征及本质进行了探讨.在MP2/6-311++G(3d,3p)水平优化、频率验证得到复合物的分子结构,通过分子的几何参数及电子密度拓扑分析,确认GeH4与卤化氢已形成了二氢键复合物.MP2/6-311++G(3d,3p)水平下进行BSSE校正后的结合能为3.281到4.502 kJ.mol-1.自然键轨道分析表明,静电作用在二氢键中起一定作用.对H(5)—X键,分子间超共轭作用与静电吸引作用产生的红移效应超过重极化和重杂化产生的蓝移效应导致H(5)—X键红移;对Ge—H键,负重极化及负重杂化与H(4)(Ge)和H(5)(X)的静电吸引作用一致,导致Ge—H(4)键拉长与振动频率红移.The intermolecular complexes of GeH4 with hydrohalides were examined using ab initio calculations performed at the second-order MФller-Plesset perturbation approximation with the 6-311 ＋＋ G（3 d, 3p ） basis set. Dihy- drogen-bonds were formed in the complexes of GeH4 with hydrohalides judged from the geometrical criteria. The characteristics of the bond critical points-the electron densities and their laplacians-also confirm this conclusion. The calculated binding energies of the complexes using MP2/6-311 ＋＋ G（3d, 3p ） methods, corrected by basis-set superposition error are 3.28 to 4.502 k J· mol^- 1. The analysis of natural bond orbital shows that the electrostatic interaction plays a role in the formation of dihydrogen-bonds. For H（5）--X bond,the red shift caused by intremolecular hyperconjugation and electrostatic attraction is greater than blue shift caused by repolarization and rehybridization, resulting in red shift of H （5）--X bond. For Ge---H bond, negative repolarization and negative rehybridization are consistent with the electrostatic attraction, resulting in Ge---H（4） bond stretching and vibration frequency red shift.

关 键 词：二氢键 分子中原子理论(AIM) 自然键轨道理论(NBO) GeH4 卤化氢 

分 类 号：O641[理学—物理化学]